KR20120116838A - Organic light compound and organic light device using the same - Google Patents

Abstract

PURPOSE: An organic electroluminescence compound is provided to provide high luminous efficiency, high brightness, high color purity and remarkably improved lifetime. CONSTITUTION: An organic electroluminescence compound comprises a first electrode, a second electrode, and at least one organic layer inserted between the first electrode and the second electrode. The organic layer comprises an organic electroluminescence compound represented by chemical formula F. In chemical formula F, X is O, S, SE or Si, each of R, A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2 is selected from H, D, F, C1-40 alkyl, C5-40 aryl, C5-40 heteroaryl, C5-40 arloxy, C1-40 alkyloxy, C5-40 arylamino, C6-40 arylalkyl, C5-40 ketone, C5-40 arylketone, C3-40 cycloalkyl and C3-40 heterocycloalkyl, or a group forming a fused aliphatic ring, fused aromatic ring, fused heteroaliphatic ring or fused heteroaromatic ring together with a neighboring group.

Description

Organic light emitting compound and organic optical device using the same {ORGANIC LIGHT COMPOUND AND ORGANIC LIGHT DEVICE USING THE SAME}

The present invention relates to an organic light emitting compound and an organic optical device using the same, and more particularly, an oxanthene derivative derived from the phosphorescent host material having excellent charge transport characteristics and well overlapping with absorption spectra of a dopant, and organic using the same. A light emitting device or an optical device for photovoltaic power generation.

In 1987, Tang et al. Developed a low-molecular-weight OLED display with rapid efficiency and stability since it discovered a green luminescent phenomenon with improved efficiency and stability by forming a bilayer low-molecular organic thin film of Alq ₃ and TPD as a light emitting layer and a charge transport layer, respectively lost. In the late 1980s, the structure of a low-molecular OLED device started from a simple structure of an anode (ITO), a hole transport layer (HTL), an emission layer (EML), and a cathode (Mg: Ag). In the case of fluorescent devices, Hole Injection Layer (HIL) such as CuPc was introduced, Al: Li was developed as cathode and electron injection layer material, and materials such as LiF were developed and the structure became complicated. Accordingly, the efficiency and driving voltage of the electro-optical characteristics have been improved.

Phosphorescent structure is generally composed of anode, hole injection layer, hole transport layer, light emitting layer, electron transfer layer (ETL), electron injection layer (EIL), and cathode (Cathode) Although a hole blocking layer (HBL) layer has been introduced, it is known that it is not necessary.

The light emitting layer material is largely classified into a light emitting material for a fluorescent device and a light emitting material for a phosphorescent device, and is further classified according to a light emitting color. The light emitting layer material is divided into a host material and a dopant material. Although only the host or dopant material can emit light, its efficiency and brightness are very low due to its own quenching phenomenon, and because of self-aggregation of molecules, each of them exhibits the characteristics of each molecule, not the unique characteristics of each molecule. In order to increase the dopant to the host to make a light emitting layer.

As a phosphorescent host material, CBP, a bipolar material having hole mobility and electron mobility, has been widely used for red and green. Recently, however, Balq or similar Al complex materials with electron transport properties are known to be useful as phosphorescent red hosts. In addition, CBP derivatives and Artsi-based materials are known to have excellent properties as blue phosphorescent host materials.

The characteristics required for the host material should first be excellent in the charge transport characteristics. Since holes and electrons must be moved in the light emitting layer, proper mobility is necessary. In addition, since the host material must transfer energy to the dopant, energy transfer occurs well when the host's emission spectrum overlaps with the absorption spectrum of the dopant. In terms of energy, the band gap of the host should be wider than the gap of Dopant, and the LUMO level of the host should be higher than the Dopant LUMO.

Therefore, in order to further improve the characteristics of the organic EL device, there is a continuous need for a more stable and efficient material that can be used as an electron transporting material in the organic EL device.

The technical problem to be achieved by the present invention is to provide a new organic optical compound that can be applied to an organic optical device, in particular an organic electroluminescent device.

Another technical problem to be achieved by the present invention is to develop an oxanthene-based derivative having excellent charge transport characteristics as a phosphorescent host material and well overlapping with the absorption spectrum of Dopant, thereby improving luminous efficiency, low voltage driving, and excellent color expression rate. It is to provide a material that implements.

The organic optical compound according to the present invention and the organic optical device using the same are based on the organic optical compound of formula F:

<Formula F>

In the formula, X is O, S, Se or Si,

A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2 are each independently

H, D, F, C1-C40 alkyl group, C5-C40 aryl group, C5-C40 heteroaryl group, C5-C40 aryloxy group, C1-C40 alkyloxy group, C5-C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C5 ~ C40 ketone group, C5 ~ C40 arylketone group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group or ; Or a group which forms a fused aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, or a condensed heteroaromatic ring with an adjacent group, provided that A1 and A2 are zero when X is O, S or Se. to be).

In addition, the organic optical compound and the organic optical device using the same according to the present invention is based on the organic optical compound corresponding to the formula 1 to 82.

The organic optical device according to the present invention provides high luminous efficiency, high luminance, high color purity and remarkably improved luminous lifetime,

In addition, the present invention provides an organic light emitting device and an organic light emitting compound, or an organic optical device and a photo compound for photovoltaic power generation.

Hereinafter, the present invention will be described in detail.

The present invention may be modified in various ways and may have various forms, and thus embodiments (or embodiments) will be described in detail in the text. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, the term &quot; comprising &quot; or &quot; consisting of &quot;, or the like, refers to the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

In particular, the present invention has developed an oxanthene derivative to be used in various ways such as various organic films between the first electrode and the second electrode, such as an electron transport layer (ETM), a light emitting layer (EML), a hole transport layer (HTM), etc. This material is a phosphorescent host material, which has excellent charge transport properties and presents a material that overlaps well with Dopant's absorption spectrum, and improves performance such as increased efficiency and reduced driving voltage and maximizes its ability as an OLED material. We want to develop

In the present specification, an organic photochemical compound is a compound used in an organic optical device, and is not necessarily limited to a compound capable of emitting light, and its application range is not limited to an organic light emitting layer, and an organic photonic compound such as a charge injection layer and a charge transport layer It can be used in any layer that constitutes the ruler.

In this specification, the terms 'optical compound' and 'optical device' are used to cover the case where the present invention is applied to both an organic light emitting device and a device for solar power generation regardless of a dictionary or conventional definition It is a selected term.

An organic photonic device according to a first aspect of the present invention includes: a first electrode; A second electrode; And an organic optical device including at least one organic film between the first electrode and the second electrode, wherein the organic film includes an organic photo compound of Formula (F).

<Formula F>

In the derivative of the formula X is O, S, Se or Si,

A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2 are each independently

H, D, F, C1-C40 alkyl group, C5-C40 aryl group, C5-C40 heteroaryl group, C5-C40 aryloxy group, C1-C40 alkyloxy group, C5-C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C5 ~ C40 ketone group, C5 ~ C40 arylketone group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group or ; Or a group which forms a fused aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, or a condensed heteroaromatic ring with an adjacent group, provided that A1 and A2 are zero when X is O, S or Se. to be).

The inventor of the present invention selects A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2 and X in the substituent of the organic photochemical compound of Formula F,

Developed various derivatives, such as an electron transport layer (ETM), light emitting layer (EML), hole transport layer (HTM), such as organic photo compounds that can be used as various organic films between the first electrode and the second electrode and

Develop an organic optical device using the same,

When used as an organic light emitting device, it has been found that performance improvement such as increased efficiency and driving voltage can be improved, and the ability as an OLED material can be maximized, and in particular, the light emission life is significantly improved.

If this is applied to photovoltaic devices and photochemical fields for photovoltaic power generation, it is expected to obtain excellent power generation efficiency.

Hereinafter, an organic photochemical compound of Formula F will be described with reference to an organic light emitting device, but the present invention should not be construed as a limitation.

The organic photochemical compound of Formula F is suitable as a material forming an organic film interposed between the first electrode and the second electrode of the organic optical device. The organic photochemical compound of Formula F is suitable for use in an organic film of an organic light emitting device, in particular, a hole transport layer, a hole injection layer or a light emitting layer, and is used as a dopant material as well as a host material. The organic photochemical compound of Formula F provides a color which is blue to green and is suitable for use in white light emitting devices.

One or more of the A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2 is C5 ~ C40 aryl group, C5 ~ C40 heteroaryl group, C5 ~ C40 arylamino group, C5 ~ C40 Diarylamino group, C6 ~ C40 arylalkyl group, C5 ~ C40 aryl ketone group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group; Or a group which forms a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring with an adjacent group,

A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2, C1 to C40 alkyl group, C5 to C40 aryl group, C5 to C40 heteroaryl group, C5 to C40 aryloxy group , C1-C40 alkyloxy group, C5-C40 arylamino group, C5-C40 diarylamino group, C6-C40 arylalkyl group, C5-C40 ketone group, C5-C40 aryl ketone group, C3-C40 Cycloalkyl group and C3-C40 heterocycloalkyl group

Each independently D, F, halogen, nitrile group, nitro group, C1 ~ C40 alkyl group, C2 ~ C40 alkenyl group, C1 ~ C40 alkoxy group, C1 ~ C40 amino group, C3 ~ C40 cycloalkyl group, C3 ~ It is preferably substituted or unsubstituted with one or more selected from the group consisting of C40 heterocycloalkyl group, C6 ~ C40 aryl group and C5 ~ C40 heteroaryl group.

A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2, C1 to C40 alkyl group, C5 to C40 aryl group, C5 to C40 heteroaryl group, C5 to C40 aryloxy group , C1-C40 alkyloxy group, C5-C40 arylamino group, C5-C40 diarylamino group, C6-C40 arylalkyl group, C5-C40 ketone group, C5-C40 aryl ketone group, C3-C40 Cycloalkyl group and C3-C40 heterocycloalkyl group

Each independently D, F, halogen, nitrile group, nitro group, C1 ~ C40 alkyl group, C2 ~ C40 alkenyl group, C1 ~ C40 alkoxy group, C1 ~ C40 amino group, C3 ~ C40 cycloalkyl group, C3 ~ It is preferable to be substituted or unsubstituted with one or more selected from the group consisting of C40 heterocycloalkyl group, C6 ~ C40 aryl group and C5 ~ C40 heteroaryl group,

And A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2, C1 to C40 alkyl group, C5 to C40 aryl group, C5 to C40 heteroaryl group, C5 to C40 aryl jade C1 ~ C40 alkyloxy group, C5 ~ C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C5 ~ C40 ketone group, C5 ~ C40 arylketone group, C3 ~ C40 Of substituents to be introduced into the cycloalkyl group and C3 to C40 heterocycloalkyl group

C1 ~ C40 alkyl group, C2 ~ C40 alkenyl group, C1 ~ C40 alkoxy group, C1 ~ C40 amino group, C3 ~ C40 cycloalkyl group, C3 ~ C40 heterocycloalkyl group, C6 ~ C40 aryl group and C5 ~~ C40 heteroaryl group

Each independently D, F, halogen, nitrile group, nitro group, C1 ~ C40 alkyl group, C2 ~ C40 alkenyl group, C1 ~ C40 alkoxy group, C1 ~ C40 amino group, C3 ~ C40 cycloalkyl group, C3 ~ Further substituted with at least one second substituent selected from the group consisting of C40 heterocycloalkyl group, C6 ~ C40 aryl group and C5 ~ C40 heteroaryl group; Or it is preferable to form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring with an adjacent group or to form a spiro bond.

Further A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2, C1 to C40 alkyl group, C5 to C40 aryl group, C5 to C40 heteroaryl group, C5 to C40 aryl jade C1 ~ C40 alkyloxy group, C5 ~ C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C5 ~ C40 ketone group, C5 ~ C40 arylketone group, C3 ~ C40 Substituents to be introduced into the cycloalkyl group and C3 to C40 heterocycloalkyl group

D, F, phenyl group, tolyl group, biphenyl group, pentalenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, benzoanthracenyl group, azurenyl group, heptarenyl group, acenaphthylyl group, phenna Renyl group, methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, pisenyl group, perrylenyl group, chloroperylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexa Phenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, fluorenyl group, pyrantrenyl group, obarenyl group, carbazolyl group, dibenzofuranyl group, dibenzo Thiophenyl group, thiophenyl group, indolyl group, furinyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrroylyl group, pyrazolyl group, imidazolyl group, imidazolinyl group, oxazolyl group , Thiazolyl group, triazolyl group, tetrazolyl group, oxadiazolyl group, Pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thianthrenyl, cyclopentyl, cyclohexyl, oxiranyl, pyrrolidinyl, pyrazolidinyl, imidazolidi It is preferable to select from the group consisting of a silyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a di (C6-C50 aryl) amino group, a silane group and derivatives thereof.

The aryl group is a monovalent group having an aromatic ring system, and may include two or more ring systems, and the two or more ring systems may exist in a bonded or condensed form with each other. The heteroaryl group refers to a group in which at least one carbon of the aryl group is substituted with at least one selected from the group consisting of N, O, S, P, Si, and Se.

Meanwhile, a cycloalkyl group refers to an alkyl group having a ring system, and the heterocycloalkyl group refers to a group in which at least one carbon of the cycloalkyl group is substituted with at least one selected from the group consisting of N, O, S, P, Si, and Se. .

When one or more hydrogen of the aryl group and heteroaryl group is substituted, their substituents are C1-C50 alkyl group; C1-C50 alkoxy group; A C6-C50 aryl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; C2-C50 heteroaryl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; A C5-C50 cycloalkyl group which is unsubstituted or substituted by a C1-C50 alkyl group or a C1-C50 alkoxy group and a C5-C50 heterocycloalkyl group which is unsubstituted or substituted by a C1-C20 alkyl group or a C1-C20 alkoxy group, &Lt; / RTI &gt;

An organic optical device according to the first aspect of the present invention, the first electrode; A second electrode; And at least one organic film between the first electrode and the second electrode.

The organic photochemical compound used in the organic photoelectric device of the present invention may have a structure represented by the following Chemical Formulas 1 to 82 (hereinafter, the chemical formulas are omitted and only numbers are shown), but is not limited thereto.

The organic photochemical compound according to the present invention represented by the compound of Formula F may be synthesized using a conventional synthetic method, and for a more detailed synthetic route of the compound, refer to the schemes of the following Synthesis Examples. The compound of formula F is suitable for use in organic membranes of organic optical devices, in particular hole transport layers, hole injection layers or light emitting layers. The structure of the organic light emitting device according to the present invention is very diverse. The organic EL device may further include at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, a hole blocking layer, an electron blocking layer, an electron transporting layer, and an electron injecting layer between the first electrode and the second electrode.

More specifically, an embodiment of an organic light emitting device according to the present invention

First, the organic light emitting device may have a structure including a first electrode / a hole injection layer / a light emitting layer / an electron transport layer / an electron injection layer / a second electrode,

The organic light emitting device may have a structure including a first electrode / a hole injection layer / a hole transport layer / a light emitting layer / an electron transport layer / an electron injection layer / a second electrode,

Further, the organic light emitting device may have a structure of a first electrode / a hole injection layer / a hole transport layer / a light emitting layer / a hole blocking layer / an electron transport layer / an electron injection layer / a second electrode.

In this case, at least one of the hole transport layer, the hole injection layer and the light emitting layer may include a compound according to the present invention.

The light-emitting layer of the organic optical device according to the present invention may include a phosphorescent or fluorescent dopant including red, green, blue or white. Among these, the phosphorescent dopant may be an organometallic compound including at least one element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, and Tm. In addition, the compound according to the present invention can also be used as a fluorescent dopant in the light emitting layer.

Hereinafter, a method of manufacturing an organic optical device according to the present invention will be described with reference to an organic optical device. First, a first electrode material having a high work function on the substrate is formed by a deposition method or a sputtering method to form a first electrode. The first electrode may be an anode. Herein, a substrate used in a conventional organic optical device is used, and a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness is preferable. Indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used as the material for the first electrode.

Next, a hole injection layer HIL may be formed on the first electrode by using various methods such as vacuum deposition, spin coating, casting, and LB.

When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal characteristics of the desired hole injection layer, and the like. In general, A degree of vacuum of 10 &lt; ^-5 &gt; to 10 &lt; ^-3 &gt; torr, a deposition rate of 0.01 to 100 A / sec and a film thickness of 100 to 1 mu m.

When the hole injection layer is formed by the spin coating method, the coating conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal properties of the desired hole injection layer, but the coating speed is preferably from about 2000 rpm to 5000 rpm , And the heat treatment temperature for removing the solvent after coating is suitably selected within a temperature range of about 80 캜 to 200 캜.

The hole injection layer material may be a compound having Formula a as described above.

Or phthalocyanine compounds such as copper phthalocyanine disclosed in US Pat. No. 4,356,429 or the starburst type amine derivatives described in Advanced Material, 6, p.677 (1994), for example, TCTA, m-MTDATA, m-. MTDAPB, 2-TNATA (4,4 ', 4 "-tris (N- (2-naphtyl) -N-phenylamino) triphenylamine: 4,4,4-tris (N- (naphthyl) -N-phenylamino) Triphenylamine), Pani / DBSA (Polyaniline / Dodecylbenzenesulfonic acid: polyaniline / dodecylbenzenesulfonic acid) or PEDOT / PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): poly (soluble conductive polymer) 3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), PANI / CSA (Polyaniline / Camphor sulfonicacid: polyaniline / camphorsulfonic acid) or PANI / PSS

(Polyaniline) / poly (4-styrenesulfonate): polyaniline) / poly (4-styrenesulfonate)) and the like can be used.

The thickness of the hole injection layer may be about 100 Å to 10000 Å, preferably 100 Å to 1000 Å. This is because when the thickness of the hole injection layer is less than 100 kV, the hole injection characteristic may be lowered, and when the thickness of the hole injection layer exceeds 10000 kV, the driving voltage may increase.

Alternatively, the hole injection layer may be formed by vacuum vapor deposition. Although specific deposition conditions depend on the compound used, they are selected from the range of conditions substantially the same as the formation of a general hole injection layer. For example, DNTPD (N, N-bis- [4- (di-m-tolylamino) phenyl] -N, N-diphenylbiphenyl-4,4-diamine) may be used.

Next, a hole transport layer (HTL) may be formed on the hole injection layer by using various methods such as vacuum deposition, spin coating, cast, and LB. In the case of forming the hole transporting layer by the vacuum deposition method and the sputtering method, the deposition conditions and the coating conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

The hole transport layer material may include a compound of Formula a as described above. Or carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole and the like, N, N'-bis (3-methylphenyl) -N, N'- diphenyl- [ Amine having an aromatic condensed ring such as N, N'-tetramethyldisiloxane, -4,4'-diamine (TPD) and N, N'-di (naphthalen- The hole transporting layer may have a thickness of about 50 Å to 1000 Å, preferably 100 Å to 600 Å. When the thickness of the hole transporting layer is less than 50 Å, the hole transporting property may be degraded. When the thickness of the hole transporting layer is more than 1000 Å, the driving voltage may increase.

Next, the light emitting layer EML may be formed on the hole transport layer by using a vacuum deposition method, a spin coating method, a cast method, an LB method, or the like. When the light emitting layer is formed by the vacuum deposition method or the spin coating method, the deposition conditions vary depending on the compound used, but are generally selected from the ranges of conditions substantially the same as those of forming the hole injection layer.

The luminescent layer may comprise a compound of formula (a) according to the invention as described above. At this time, the compound of formula a may be used with a suitable known host material or may be used with a known dopant material.

It is also possible to use the compound of formula (A) alone. In the case of the host material, for example, Alq3 (tris (8-hydroxy-quinolatealuminium) or CBP (4,4'-N, N'-dicarbazole- ) Can be used.

In the case of the dopant material, IDE102, IDE105 and IDE55 available from Idemitsu Co., Ltd. and C545T available from Hayashibara Co., Ltd. can be used. As the phosphorescent dopant, red phosphorescent dopant PtOEP, UDC RD61, green phosphorescent dopant Ir (PPy) 3 (PPy = 2-phenylpyridine), a blue phosphorescent dopant F2Irpic, and a red phosphorescent dopant RD 61 manufactured by UDC. MQD (N-methylquinacridone), coumarine derivatives and the like can also be used.

The doping concentration is not particularly limited, but the content of the dopant is generally 0.01 to 15 parts by weight based on 100 parts by weight of the host. The thickness of the light emitting layer may be about 100 kPa to 1000 kPa, preferably 200 kPa to 600 kPa.

When the thickness of the light emitting layer is less than 100 Å, the light emitting characteristics may be degraded. If the thickness of the light emitting layer is more than 1000 Å, the driving voltage may increase.

When a luminescent compound is used together with a phosphorescent dopant in the luminescent layer, a method such as vacuum deposition, spin coating, casting, LB or the like is performed on the luminescent layer to prevent the triplet excitons or holes from diffusing into the electron transporting layer The hole blocking layer HBL can be formed. In the case of forming the hole blocking layer by the vacuum deposition method and the spin coating method, the conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer. Known hole blocking materials that can be used include, for example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and BCP.

The hole blocking layer may have a thickness of about 50 kPa to 1000 kPa, preferably 100 kPa to 300 kPa. If the thickness of the hole blocking layer is less than 50 angstroms, the hole blocking characteristics may be deteriorated. If the thickness of the hole blocking layer exceeds 1000 angstroms, the driving voltage may be increased. An organic light emitting element having the structure shown in FIG. 1B is obtained.

Next, an electron transport layer (ETL) is formed by various methods such as a vacuum evaporation method, a spin coating method, and a casting method.

When the electron transport layer is formed by the vacuum deposition method or the spin coating method, the conditions vary depending on the compound used, but are generally selected from the ranges of conditions almost the same as that of the formation of the hole injection layer. The electron transport layer material serves to stably transport electrons injected from an electron injection electrode, and is a quinoline derivative, particularly a known material such as tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, Materials may also be used.

The electron transport layer may have a thickness of about 100 kPa to 1000 kPa, preferably 200 kPa to 500 kPa. When the thickness of the electron transporting layer is less than 100 angstroms, the electron transporting characteristics may be deteriorated. When the thickness of the electron transporting layer exceeds 1000 angstroms, the driving voltage may increase.

Further, an electron injection layer (EIL), which is a material having a function of facilitating the injection of electrons from the cathode, may be laminated on the electron transporting layer, which is not particularly limited.

As the electron injection layer, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li 2 O, BaO or the like can be used. The deposition conditions of the electron injection layer vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

The thickness of the electron injection layer may be about 1 A to 100 A, preferably 5 A to 50 A. This is because, when the thickness of the electron injection layer is less than 1 kW, the electron injection characteristic may be deteriorated, and when the thickness of the electron injection layer exceeds 100 kW, the driving voltage may increase.

Finally, the second electrode can be formed on the electron injection layer by a vacuum evaporation method, a sputtering method, or the like.

The second electrode may be used as a cathode. As the metal for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, and a mixture thereof may be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- . Also, a transmissive cathode using ITO or IZO may be used to obtain a front light emitting element.

The organic electroluminescent compound according to another embodiment of the present invention may be represented by Chemical Formula a, and more specifically, may be represented by Chemical Formulas 1 to 82. Details of the compounds are the same as those described for the above-mentioned organic feet and devices.

Hereinafter, the reaction examples and comparative examples of the present invention will be specifically illustrated, but the present invention is not limited to the following synthesis examples and examples. In the following reaction examples, the intermediate compounds are indicated by adding the serial number to the final product number. For example, Compound 1 is represented by the compound [1], and the intermediate compound of the above compound is represented by [1-1] or the like. In the present specification, the chemical number is represented by the chemical number. For example, the compound represented by the formula (1) is represented by compound 1.

[Reaction Example 1] Synthesis of Compound [35]

Preparation of Intermediate Compound [35-1]

In a 1 L reaction flask, 19.0 g (0.101 mol) of 2-bromothiophenol and 27.8 g (0.201 mol) of potassium carbonate are stirred with 300 mL of N, N-dimethylformamide in a nitrogen atmosphere. 14.6 mL (0.12 mol) of 2'-fluoroacetophenone is added dropwise at room temperature, and the temperature is increased, followed by stirring at 100 ° C for 12 hours. After cooling to room temperature, the reaction solution was poured into 800 mL of saturated ammonium chloride aqueous solution to separate an organic layer. The organic layer is dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized from dichloromethane and hexane to prepare 22.0 g (72%) of an intermediate compound [35-1].

Preparation of Intermediate Compound [35-2]

21.5 g (69.98 mmol) of the intermediate compound [35-1] were added to the flask, and the mixture was dissolved by stirring with 300 mL of anhydrous tetrahydrofuran in a nitrogen atmosphere. 75 mL (1.4 M, 0.104 mol) of methyl magnesium bromide was slowly added dropwise at 5 ° C. After stirring for 1 hour at the same temperature, the reaction solution was poured into 500 mL of saturated aqueous ammonium chloride solution and extracted with 300 mL of ethyl acetate. The organic layer is separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and separated and purified by silica gel column chromatography to obtain 20.0 g (93%) of an intermediate compound [35-2] as a colorless oil.

Preparation of Intermediate Compound [35-3]

20 g (61.87 mmol) of an intermediate compound [35-2] and 400 ml of methanesulfonic acid were added to a flask and stirred at 60 ° C. After completion of the reaction, the reaction solution was slowly added to a constant 1 L while stirring and the resulting solid was filtered under reduced pressure. The obtained solid was recrystallized from dichloromethane and methanol and purified by column chromatography to give 9.6 g (51%) of a white solid intermediate compound [35-3].

Preparation of Intermediate Compound [35-4]

9.1 g (29.81 mmol) of an intermediate compound [35-3] and 150 ml of tetrahydrofuran are added to the flask, followed by stirring under N ₂ to dissolve completely. 14.3 ml (35.77 mmol) of 2.5M n-butyllithium was slowly added dropwise at -78 ° C, and 3.99 ml (35.77 mmol) of trimethylborate was added dropwise at the same temperature after 30 minutes. After completion of the reaction, poured into 1N aqueous hydrochloric acid solution at room temperature and extracted with ethyl acetate. After separation of the organic layer, recrystallization with dichloromethane and normal hexane afforded 4.7 g (59%) of an intermediate compound [35-4] as a white solid.

Preparation of Intermediate Compound [35-5]

4.2 g (15.54 mmol) of intermediate compound [35-4], 4.4 g (15.54 mmol) of 1-bromo-3-iodovangen, 2.79 g (20.21 mmol) of calcium carbonate, tetrakis (triphenylphosphine) 0.18 g (0.15 mmol) of palladium was added thereto, and the mixture was stirred under reflux for 12 hours with toluene and purified water under nitrogen. After completion of the reaction, the organic layer was extracted with ethyl acetate at room temperature, dried over anhydrous magnesium sulfate, and filtered. The solid obtained was separated and purified through column chromatography to obtain 3.7 g (63%) of an intermediate compound [35-5]. .

Preparation of Compound [35]

3.3 g (8.65 mmol) of intermediate compound [35-5], 2.6 g (9.52 mmol) of 2-triphenyleneboronic acid, 1.55 g (11.25 mmol) of calcium carbonate, and 0.1 g of tetrakis (triphenylphosphine) palladium 0.08 mmol), and the mixture is stirred under reflux with toluene and purified water for 12 hours under nitrogen. After completion of the reaction, the recrystallized solid was filtered off under reduced pressure at room temperature in dichloromethane and methanol and the purified by column chromatography to give the desired compound [35] 3.4g (76%) of a white solid.

Compounds 1 to 82 were prepared in the same manner as in Reaction Example 1, and the results are shown in the following [Table 1].

[First vote group]

Comparative Example 1

Using compound a represented by the following formula a as a phosphorescent blue host, and a compound represented by the following formula b as a phosphorescent blue dopant, 2-TNATA (4,4 ', 4 ”-tris (N-naphthalen-2 -yl) -N-phenylamino) -triphenylamine) is used as the hole injection layer material, and α-NPD (N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine) is used as the hole transport layer material. Using the same structure, an organic light emitting device was manufactured: ITO / 2-TNATA (80 nm) / α-NPD (30 nm) / Compound a + Compound b (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm).

Anode cuts Corning's 15Ω / cm ² (1000Å) ITO glass substrate into 50mm x 50mm x 0.7mm sizes, ultrasonically cleans for 15 minutes in acetone isopropyl alcohol and pure water, and then UV ozone for 30 minutes. It was used by washing. 2-TANATA was vacuum-deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer,? -NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. Compound a represented by Formula a and Compound b represented by Formula b (8% doping) were vacuum deposited on the hole transport layer to form a light emitting layer having a thickness of 30 nm. Then, an Alq3 compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. LiF 0.5 nm (electron injection layer) and Al 60 nm (cathode) were sequentially vacuum-deposited on the electron transport layer to prepare an organic light emitting device as shown in Table 3. This is referred to as Comparative Sample 1.

In this comparative example and the following comparative examples and embodiments, devices were fabricated by using an EL evaporator manufactured by DeVoiste.

<Formula a> <Formula b>

Examples 1 to 82

In Comparative Example 1, except that Compound 1 to 82 represented by Formulas 1 to 82 disclosed in Synthesis Example were used as the emitting layer phosphorescent host compound instead of Compound a as the emitting layer phosphorescent host compound, in the same manner as in Comparative Example 1 ITO / 2-TNATA (80 nm) / α-NPD (30 nm) / [Organic host compound 1-82] (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm) A light emitting device was prepared. These are called Samples 1 to 81, respectively.

Evaluation Example 1 Evaluation of Luminescence Characteristics of Comparative Sample 1 and Samples 1 to 82

For Comparative Sample 1 and Samples 1 to 82, luminescence brightness, luminescence efficiency, and luminescence peak were evaluated using Keithley SMU 235 and PR650, respectively, and the results are shown in the following [Table 2]. The samples showed green emission peaks in the range of 516-524 nm.

[2nd vote group]

As shown in [Second Table], Samples 1 to 82 showed improved luminescence properties compared to Comparative Sample 1.

Although the well-known techniques are omitted in the above description, those skilled in the art can easily infer, infer, and reproduce them.

Claims (10)

A first electrode; A second electrode; And an organic optical device comprising at least one layer of an organic film between the first electrode and the second electrode, wherein the organic film comprises an organic optical compound of formula F:
<Formula F>

In the formula, X is O, S, Se or Si,
A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2 are each independently
H, D, F, C1-C40 alkyl group, C5-C40 aryl group, C5-C40 heteroaryl group, C5-C40 aryloxy group, C1-C40 alkyloxy group, C5-C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C5 ~ C40 ketone group, C5 ~ C40 arylketone group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group or ; Or a group which forms a fused aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, or a condensed heteroaromatic ring with an adjacent group, provided that A1 and A2 are zero when X is O, S or Se. to be). The method of claim 1,
One or more of the A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2 is C5 ~ C40 aryl group, C5 ~ C40 heteroaryl group, C5 ~ C40 arylamino group, C5 ~ C40 Diarylamino group, C6 ~ C40 arylalkyl group, C5 ~ C40 aryl ketone group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group; Or a group forming a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring with an adjacent group. The method of claim 1,
A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2, C1 to C40 alkyl group, C5 to C40 aryl group, C5 to C40 heteroaryl group, C5 to C40 aryloxy group , C1-C40 alkyloxy group, C5-C40 arylamino group, C5-C40 diarylamino group, C6-C40 arylalkyl group, C5-C40 ketone group, C5-C40 aryl ketone group, C3-C40 Cycloalkyl group and C3-C40 heterocycloalkyl group
Each independently D, F, halogen, nitrile group, nitro group, C1 ~ C40 alkyl group, C2 ~ C40 alkenyl group, C1 ~ C40 alkoxy group, C1 ~ C40 amino group, C3 ~ C40 cycloalkyl group, C3 ~ An organic photo device, which is unsubstituted or substituted with one or more selected from the group consisting of C40 heterocycloalkyl group, C6 ~ C40 aryl group, and C5 ~ C40 heteroaryl group. The method of claim 1,
A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2, C1 to C40 alkyl group, C5 to C40 aryl group, C5 to C40 heteroaryl group, C5 to C40 aryloxy group , C1-C40 alkyloxy group, C5-C40 arylamino group, C5-C40 diarylamino group, C6-C40 arylalkyl group, C5-C40 ketone group, C5-C40 aryl ketone group, C3-C40 Cycloalkyl group and C3-C40 heterocycloalkyl group
Each independently D, F, halogen, nitrile group, nitro group, C1 ~ C40 alkyl group, C2 ~ C40 alkenyl group, C1 ~ C40 alkoxy group, C1 ~ C40 amino group, C3 ~ C40 cycloalkyl group, C3 ~ Further substituted with at least one second substituent selected from the group consisting of C40 heterocycloalkyl group, C6 ~ C40 aryl group and C5 ~ C40 heteroaryl group; Or an organic photo device, which forms a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, or a condensed heteroaromatic ring and a spiro bond with an adjacent group. The method of claim 1,
A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2, C1 to C40 alkyl group, C5 to C40 aryl group, C5 to C40 heteroaryl group, C5 to C40 aryloxy group , C1-C40 alkyloxy group, C5-C40 arylamino group, C5-C40 diarylamino group, C6-C40 arylalkyl group, C5-C40 ketone group, C5-C40 aryl ketone group, C3-C40 Substituents to be introduced into the cycloalkyl group and C3 to C40 heterocycloalkyl group
D, F, phenyl group, tolyl group, biphenyl group, pentalenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, benzoanthracenyl group, azurenyl group, heptarenyl group, acenaphthylyl group, phenna Renyl group, methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, pisenyl group, perrylenyl group, chloroperylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexa Phenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, fluorenyl group, pyrantrenyl group, obarenyl group, carbazolyl group, dibenzofuranyl group, dibenzo Thiophenyl group, thiophenyl group, indolyl group, furinyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrroylyl group, pyrazolyl group, imidazolyl group, imidazolinyl group, oxazolyl group , Thiazolyl group, triazolyl group, tetrazolyl group, oxadiazolyl group, Pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thianthrenyl, cyclopentyl, cyclohexyl, oxiranyl, pyrrolidinyl, pyrazolidinyl, imidazolidi An organic optical device, characterized in that selected from the group consisting of a silyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a di (C6-C50 aryl) amino group, a silane group and derivatives thereof. The method of claim 1,
An organic optical device characterized in that the compound is represented by the formula 1 to 82:

An organic light emitting compound represented by formula F:
<Formula F>

In the formula, X is O, S, Se or Si,
A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2 are each independently
H, D, F, C1-C40 alkyl group, C5-C40 aryl group, C5-C40 heteroaryl group, C5-C40 aryloxy group, C1-C40 alkyloxy group, C5-C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C5 ~ C40 ketone group, C5 ~ C40 arylketone group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group or ; Or a group which forms a fused aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, or a condensed heteroaromatic ring with an adjacent group, provided that A1 and A2 are zero when X is O, S or Se. to be). The method of claim 7, wherein
One or more of the A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2 is C5 ~ C40 aryl group, C5 ~ C40 heteroaryl group, C5 ~ C40 arylamino group, C5 ~ C40 Diarylamino group, C6 ~ C40 arylalkyl group, C5 ~ C40 aryl ketone group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group; Or a group forming a fused aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring with an adjacent group. The method of claim 7, wherein
A1, A2, B1, B2, C1, C2, D1, D2, E1 and E2, C1 to C40 alkyl group, C5 to C40 aryl group, C5 to C40 heteroaryl group, C5 to C40 aryloxy group , C1-C40 alkyloxy group, C5-C40 arylamino group, C5-C40 diarylamino group, C6-C40 arylalkyl group, C5-C40 ketone group, C5-C40 aryl ketone group, C3-C40 Cycloalkyl group and C3-C40 heterocycloalkyl group
Each independently D, F, halogen, nitrile group, nitro group, C1 ~ C40 alkyl group, C2 ~ C40 alkenyl group, C1 ~ C40 alkoxy group, C1 ~ C40 amino group, C3 ~ C40 cycloalkyl group, C3 ~ An organic light emitting compound characterized by being substituted or unsubstituted with one or more selected from the group consisting of C40 heterocycloalkyl group, C6 ~ C40 aryl group and C5 ~ C40 heteroaryl group. The method of claim 1,
An organic light emitting compound characterized in that the compound is represented by the formula 1 to 82: